CN1251348A

CN1251348A - Method for preparing nanometer material of compound of sulfur family and phosphorus family

Info

Publication number: CN1251348A
Application number: CN 98119471
Authority: CN
Inventors: 钱逸泰; 王文中
Original assignee: University of Science and Technology of China USTC
Current assignee: University of Science and Technology of China USTC
Priority date: 1998-10-15
Filing date: 1998-10-15
Publication date: 2000-04-26
Anticipated expiration: 2018-10-15
Also published as: CN1086177C

Abstract

The preparation method of chalcogenide or phosphorus family compound nanometer material is characterized by that mixing the metal salt, chalcogen or phosphorus family non-metallic elementary substance and hydroborates metered according to its chemical reaction equation in organic solvent, completely reacting, filtering, washing and drying to obtain the invented produt. Said invention is implemented at room-temp., simple in operation and easy to implement, its raw material is cheap and easily available, it can save energy source, reduce cost,and is safe in operation and applicable to large-scale production of chalcogen and phosphorus family semiconductive material.

Description

Preparation method of sulfur family phosphorus family compound nano material

The invention relates to the technical field of chemical reduction preparation methods of semiconductor nano materials, in particular to a preparation technology of selenide, phosphide, sulfide, arsenide, antimonide and telluride nano materials.

The semiconductor nano material has wide application prospect in the aspects of nonlinear optical devices, photoelectric devices, solar cells and the like. Journal of the material science (j. mater.sci., 1990, 25, 1159) and the chemical society of review (chem.soc.rev, 1996, 25, 199) in the united kingdom have reported the preparation of semiconductor materials using high temperature self-propagating reaction methods and solid phase metathesis methods, respectively, but both require high temperatures; although the method reported by "journal of chemical society, dalton journal" (j.chem.soc., dalton. trans., 1997, 231. one. 236) of royal kingdom is a room temperature reaction, the reaction needs to be carried out in liquid ammonia which is easy to explode, and the operation of the reaction in the liquid ammonia is complicated, and the obtained product has a large size, and some of the products are amorphous. At present, the chalcogen phosphorus family nanometer material is prepared by pyrolyzing metal organic precursors, but the method needs complicated and expensive instruments and equipment, and the preparation of the precursors is difficult. Borohydride has been reported as a reducing agent for preparing metal simple substances in journal of Science (Science, vol.246, 1260, 1989), but borohydride has not been reported for preparing semiconductor nanomaterials.

The invention aims to provide a method for preparing a chalcogenide or phosphorus compound nano material by borohydride reduction.

The preparation method of the nanometer material of the sulfur group or phosphorus group compound is characterized in that the metal salt MX metered according to the chemical reaction equation_nMixing the nonmetal simple substance E and borohydride in an organic solvent, reacting completely, filtering, washing and drying; wherein M is Cu, Ag, Zn, Cd, Hg, Fe, Co, Ni, Ge, Sn, Pb, Al, Ga, In, As, Sb or Bi; x is F^-、Cl^-、Br^-、I^-、NO₃ ^-Or SO₄ ^2-(ii) a n is the value of the valence of the corresponding M metal ion divided by the number of charges of the corresponding anion X; e is S, Se, Te, P, As or Sb; the borohydride is derived from LiBH₄、NaBH₄Or KBH₄Selecting; the organic solvent is selected from benzene, toluene, ethylenediamine, polyamine, pyridine, carbon disulfide, tetrahydrofuran, alcohols or ethers.

The reaction of the process of the invention can be carried out at room temperature to 200 ℃; the most important advantage is that these reactions can be carried out at room temperature and normal pressure.

Because the method of the invention dissolves metal salt and sulfur family or phosphorus family simple substance in organic solvent for reaction, compared with solid phase reaction method, the contact chance between reactants is greatly increased, and the reduction action of borohydride is added, so that the metal salt can react with the sulfur family and phosphorus family simple substance at room temperature and normal pressure, and the solvent can absorb the heat generated in the reaction process, so that the reaction can be carried out smoothly; and the solvent has the function of dissolution or complexation, so that the corresponding nano semiconductor material can be obtained.

Because the raw material MX used in the method_nThe anion X in the method does not actually participate in the reaction, so the selection range of the anion in the raw material is wider, and the method is suitable for wide selection range of the raw material; due to the organic solventThe method has the functions of dissolving or complexing, and different solvents can be selected aiming at different metal salts and sulfur group and phosphorus group simple substances to facilitate the reaction; according to the similarity of chemical properties of the same group elements of Cu, Ag, Zn, Cd, Hg, Fe, Co, Ni, Ge, Sn, Pb, Al, Ga, In, As, Sb and Bi and S, Se, Te, P, As and Sb, a series of corresponding chalcogenide or phosphorus semiconductor nano materials can be prepared by the method, so that the application range of the method is wider.

The reduction preparation method adopted by the invention can be carried out at room temperature and normal pressure, the operation is simple and easy, the raw materials are cheap and easy to obtain, the defects that high-temperature equipment and complex and expensive instruments and equipment are required to be used in the existing method are avoided, and the danger of explosion caused by using liquidammonia is avoided; the method can save energy, reduce cost and has safe operation; the method is suitable for large-scale production of chalcogenide and phosphorus semiconductor materials.

The following are examples of the present invention.

Example 1. preparation of nano silver selenide material at room temperature:

reaction formula is

Selecting a glass bottle with a ground stopper and a capacity of 100mL, firstly filling 20mL of ethylenediamine into the bottle, and then weighing 0.85 g of AgNO by using a balance₃0.40 g selenium powder and 0.20 g KBH₄Putting the mixture into a bottle, tightly plugging the ground stopper, and quickly generating black precipitates in the solution; standing at room temperature for about 4 hours until colorless AgNO₃The crystals completely disappeared and no black precipitate increased, the ground bottle was opened, the resulting precipitate was filtered, washed with water and air dried naturally at room temperature to obtain 0.66 g of product. The obtained product is determined to be pure Ag by X-ray powder diffraction method₂Se; the particles were observed by an electron microscope to be spherical particles having a particle diameter of 15. + -.2 nm.

With CuCl₂In place of the above AgNO₃By the same method as above, Cu can be obtained₂Se nano material, Cu of sheet shape characterized by transmission electron microscope₂Se nano material.

Example 2 preparation of nano cadmium selenide material at room temperature:

reaction formula is

Selecting a glass bottle with a ground stopper and a capacity of 100mL, firstly filling 20mL of ethylenediamine into the bottle, and then weighing 0.90 g of CdCl₂0.40 g selenium powder and 0.20 g KBH₄Placing into a bottle, plugging the ground stopper, allowing black precipitate to appear in the solution quickly, standing at room temperature for 4 hr, and collecting white granular CdCl₂The starting material disappeared completely and the black precipitate did not increase any more, the ground bottle was opened and the precipitate was filtered, washed with water and dried naturally at room temperature to obtain 0.83 g of product. The obtained product was measured by X-ray powder diffraction method and was determined to bePure CdSe; the average particle size can be calculated to be 10nm from the broadening of diffraction peaks according to the Sherle formula; the product is observed by an electron microscope, and is known as particles with the particle size of 10 +/-3 nm, and the shape of the particles is rod-shaped.

Respectively with ZnCl₂、NiCl₂、PbCl₂And SnCl₂In place of the above-mentioned CdCl₂The ZnSe, NiSe, PbSe and SnSe nano materials can be respectively prepared by adopting the same method.

Example 3 room temperature preparation of nano bismuth selenide material:

reaction formula is

Selecting a glass bottle with a ground stopper and a capacity of 100mL, firstly filling 20mL of ethylenediamine into the bottle, and then weighing 1.6 g of BiCl₃0.6 g selenium powder and 0.8 g KBH₄Placing into a bottle, plugging the ground stopper, allowing black precipitate to appear in the solution quickly, standing at room temperature for 4 hr, and collecting white powder BiCl₃The starting material disappeared completely and the black precipitate did not increase anymore, the ground bottle was opened and the precipitate obtained was filtered, washed with water and dried naturally at room temperature to obtain 1.6 g of product. The obtained product was measured by X-ray powder diffraction method to determine pure Bi₂Se₃(ii) a The average particle size can be calculated from the broadening of diffraction peaks according to the Sherle formula to be 20 nm; the product is observed by an electron microscope, and the particle size is 20 +/-3 nm, and the shape of the particle is rod-shaped.

Respectively with AsCl₃And SbCl₃In place of the above BiCl₃As obtained by the same method As above₂Se₃And Sb₂Se₃And (3) nano materials.

Example 4 preparation of nano indium phosphide material at room temperature:

reaction formula is

Selecting a glass bottle with a ground opening and a capacity of 100mL, filling 20mL of absolute ethyl alcohol into the bottle, and weighing 1.10 g of InCl₃0.20 g of white phosphorus and 0.1 g of KBH₄Putting the mixture into a bottle, tightly plugging the ground stopper, and allowing black precipitates to appear in the solution after about 10 minutes; after standing at room temperature for 12 hours, the black precipitate does not increase any more, the ground bottle is opened, the obtained precipitate is filtered, washed with dilute hydrochloric acid with the concentration of 0.5mol/L, washed with distilled water and naturally dried at room temperature to obtain 0.50 g of product. Determining the InP as pure InP by X-ray powder diffraction method; according to the scherrer equation, the average particle size was 15nm as calculated from the broadening of the diffraction peak.

With NiCl₂Instead of InCl₃Ni having an average particle diameter of 20nm can be obtained in the same manner as described above₂P。

Claims

1. A process for preparing the nano material of sulfur family or phosphorus family features that the metal salt MX is proportionally prepared from the metal salt MX_nMixing the nonmetal simple substance E and borohydride in an organic solvent, reacting completely, filtering, washing and drying; wherein M is Cu, Ag, Zn, Cd, Hg, Fe, Co, Ni, Ge, Sn, Pb, Al, Ga, In, As, Sb or Bi; x is F^-、Cl^-、Br^-、I^-、NO₃ ^-Or SO₄ ^2-(ii) a n is the value of the valence of the corresponding M metal ion divided by the number of charges of the corresponding anion X; e is S, Se, Te, P, As or Sb; the borohydride is derived from LiBH₄、NaBH₄Or KBH₄Selecting; the organic solvent is selected from benzene, toluene, ethylenediamine,Polyamine, pyridine, carbon disulfide, tetrahydrofuran, alcohols or ethers.